Premixed hybrid grout

ABSTRACT

Grouts, grout products and methods of applying such grouts that include a urethane-acrylic hybrid polymer dispersion (UA-HPD) and a filler material. The UA-HPD may be present in an amount of about 10-40% by weight of the composition, while the filler material may be present in an amount of about 60-90% by weight of the composition. Additional filler materials may also be provided within the UA-HPD grout composition to provide the resultant UA-HPD grout with desired characteristics and properties. The UA-HPD containing grouts are applied between spaced-apart tiles and/or masonry to fill voids and/or joints there-between.

CROSS REFERENCE TO RELATED APPLICATIONS

This invention disclosure claims priority from U.S. provisional patentapplication No. 61/829,143 filed May 30, 2013.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention is directed to grout, and in particular, topremixed grouts containing a urethane/acrylic hybrid constituent as anactive binding agent in the composition, and methods of using thepremixed urethane/acrylic hybrid grouts of the invention.

2. Description of Related Art

Various types of grouts exist in today's market for a wide variety ofapplications. A common usage of grouts is in the construction industry,and in particular, for use in joining tile, masonry and other types ofbuilding materials, as well as for filling joints and voids between suchmaterials. Grouts exist in different forms including, for instance,cement-based grouts, polymer modified cement-based grouts, two-partpolymer grouts (e.g., epoxy grouts), and one-part polymer grouts. Eachof these types of grouts has its advantages and disadvantages.

Cement-based grouts are relatively low cost, easy to apply, andeventually cure into a very hard surface. One of the more common andcost effective cement-based grout is Portland cement. While cement-basedgrouts are advantageously low cost and readily available in the marketplace, one of the primary drawbacks of such grouts is in their mixingand slow-strength development. In mixing cement-based grouts, acement-based material (e.g., a cementitious powder) is combined withwater or a latex modifier (e.g., to form a polymer modified cement-basedgrout), which must then be well blended. A mechanical mixer is oftenrequired to blending these cement-based mixtures, whereby such mixersmay be costly and difficult to operate. Mixing via a mechanical mixer isalso time-consuming process, messy, and often generates large amounts ofdust. Other disadvantages of cement-based grouts are that they can oftenbe non-uniform in color and even have poor stain resistance once cured.

Two-part polymer grouts exist as an alternative to cement-based groutsand/or polymer modified cement-based grouts. While two-part polymergrouts may have higher performance criteria, as compared to cement-basedand/or polymer modified cement-based grouts, two-part grouts are oftendifficult to implement since such compositions must be used immediatelyafter mixing. In these two-part polymer grout systems, the first andsecond parts must be combined in an appropriate ratio and mixedimmediately prior to application. Once mixed, the two-part groutcomposition cures rather quickly, and as such, must be used in arelatively short period of time. Any unused portion of the two-partgrout composition is generally wasted.

Epoxy-based grouts are an example of a two-part polymer grout systems,and may even be provided in the form of a three-part grout compositionor system. While such epoxy grouts are often hard and resistant tochemicals and stains, drawbacks thereof are the multiple parts of suchsystems that require mixing as described above. Epoxy-based grouts canbe extremely toxic, and often more expensive as compared to alternativegrout materials.

As an alternative to grouts requiring mixing, currently available groutsalso include premixed and/or one-part grout compositions. Since theycome ready to use in a pre-mixed state, these types of grouts are ofteneasier to use than cementitious grouts and/or two- or three-part groutsystems. One of the biggest advantages of such premixed grouts is thatthey do not need to be mixed with other constituent(s) prior to usethereof, which aids in their ease of use. Currently available premixedgrouts are also relatively safe and do not generate dust.

A grout installer is provided with a longer time to work with premixedgrouts since these types of grouts harden or cure primarily upon drying.In comparison, cementitious grouts often begin to cure or harden uponaddition of the aqueous phase (e.g., water), while two-part polymergrouts often begin to cure and harden upon the blending of such twoparts. The longer dry time of premixed grouts provides the installerample time to work with such grouts. Yet, this longer time dry or curetime can also be seen as a disadvantage since premixed grouts are slowto develop strength. The cure or hardening mechanism for these materialsis through loss of moisture (e.g., water), which can take several daysto cure properly. As such, hardening in cool or humid environments issignificantly slowed. Due to this moisture loss, several conventionalpremixed grouts are also susceptible to shrinkage and/or cracking,particularly, when used with water-absorbing materials (e.g., claytiles). Another disadvantage is that the currently available premixedgrouts are often susceptible to staining.

Several premixed grout compositions exist in the market. For instance,currently available premixed grouts include those containing awater-based dispersion or latex polymer, along with fillers, thickenersand modifiers (e.g., defoamers, surfactants). The water-based dispersionor latex polymer is typically a thermoplastic resin, and is used as abinder in the system. The composition is applied to grout joints andallowed to cure by drying to provide hardness and strength to theapplied grout.

Premixed grouts having an acrylic binder (e.g., acrylic polymers andcopolymers) were among some of the first premixed grouts commerciallyavailable. These types of acrylic binder premixed grouts are designedfor use in low demand applications, such as, for use in kitchenbacksplashes and/or areas that are not subjected to water. U.S. Pat.Nos. 3,859,233 and 4,472,540 (both to Barker) describe the use ofacrylic binder dispersions in grout compositions.

Other premixed grouts on the market include those containing mere simpleblends of polyurethane and acrylic. In these grouts, the polyurethaneand acrylic components reside in the composition as separateconstituents, and may be individually identified, isolated and separatedfrom such composition. In these grouts, a polyurethane component isadded to the composition to improve performance of the acrylic-basedmaterial including, for instance, improving hardness, abrasionresistance and stain resistance of the resultant grout. U.S. Pat. No.5,569,696 (to Abramson, et al.) discloses such a premixed groutcontaining a blend of a polyurethane part in combination with an acrylicpart.

In further developments, polyurethane dispersion (i.e., a waterbournepolyurethane) grouts were introduced into the market. These types ofpremixed grouts contain the polyurethane dispersion as the active binderin the composition. U.S. Pat. No. 7,183,338 (to Warren) describes groutsand grout products including waterbourne polyurethane binder systems.Polyurethane dispersion grout formulations generally exhibit improvedperformance criteria over that of acrylic binder grout systems or suchgrouts blended with polyurethane. For instance, polyurethane(waterbourne polyurethane) binder grouts exhibit increased waterresistance, hardness, durability and flexibility, as well as enhancedstain resistance. However, these polyurethane dispersion (waterbornepolyurethane) grouts continue to have long cure or hardening times, areexpensive, and continue to need improved overall performancecharacteristics.

While many developments have been made in the grout industry, therecontinues to be a need for improved grout compositions having increasedhardness, strength, durability, flexibility, water resistance, stainresistance, and even faster cure/hardening times as compared to theabove discussed prior art grouts.

SUMMARY OF THE INVENTION

Bearing in mind the problems and deficiencies of the prior art, it istherefore an object of the present invention to provide improved groutcompositions that produce grout products having increased hardness,strength, durability, flexibility, water resistance, stain resistance,and even faster cure/hardening times as compared to the above discussedprior art grouts.

It is another object of the present invention to provide groutcompositions that include a urethane-acrylic hybrid polymer dispersion(UA-HPD) as a binder in combination with filler materials. The fillermaterial may be sand, silica sand, colored silica sand, fine silica,glass, recycled glass, limestone, minerals, any other known filler, orany combinations thereof.

In various aspects of the invention, the UA-HPD grout formulations ofthe invention may include the UA-HPD binder in combination with a quartzfiller material, as well as one or more additional constituentsincluding, but not limited to, a freeze-thaw stabilizer co-solvent,plasticizer, short fibers, glass fibers, an adhesion promoter, apreservative, biocide, cellulose or starch ether, a thickening agent,silica fume, fumed silica, silica fume, a deaerator, defoamer, and/orsurfactant.

It is another object of the present invention to provide UA-HPD groutcompositions that include a urethane-acrylic hybrid polymer dispersion(UA-HPD) as a binder present in an amount of about 10-40% by weight ofthe composition, in combination with one or more filler materialspresent in an amount of about 60-90% by weight of the composition. Thefiller material may be sand, silica sand, colored silica sand, finesilica, glass, recycled glass, limestone, minerals, any other knownfiller, or any combinations thereof. These UA-HPD grout compositions mayfurther include about 0-3 wt. % thickening agent, about 0-1 wt. %preservative, about 0-1 wt. % biocide, fungicide or mildewcide, about0-3 wt. % defoamer, about 0-10 wt. % decorative fillers, about 0-15 wt.% film forming aids, about 0-5 wt. % crosslinking agents, about 0-5 wt.% stain resistant additives, about 0-5 wt. % adhesion promoters, about0-5 wt. % coupling agents, about 0-5 wt. % anti-freeze agents, about 0-5wt. % surfactants, about 0-10 wt. % water, about 0-5 wt. % waterretention aid, about 0-5 wt. % UV stabilizers, about 0-5 wt. % acid orbase component, about 0-5 wt. % strengthening fibers, as well as anycombination of the foregoing materials.

Another aspect of the invention is directed to UA-HPD grout compositionsthat include about 19-23 wt. % urethane-acrylic hybrid polymerdispersion as a binder, about 70-80 wt. % quartz filler present, withthe remainder wt. % of the composition being one or more additionalfiller materials that add desired characteristics and properties to theUA-HPD grout compositions. The quartz filler may be glass filler orsilica sand. The additional filler materials may include one or moreconstituents comprising a freeze-thaw stabilizer co-solvent,plasticizer, short fibers, glass fibers, an adhesion promoter, apreservative, biocide, cellulose or starch ether, a thickening agent,silica fume, fumed silica, fumed silica/silica fume, a deaerator,defoamer, surfactant, and/or any combination of the foregoing.

In still another aspect, the invention is directed to methods ofapplying grout by providing spaced-apart building materials affixed to asubstrate, whereby unfilled openings reside between the spaced-apartbuilding materials. A grout comprising a one-part admixture ofurethane-acrylic hybrid polymer dispersion (UA-HPD) as a binder andfiller material is provided and applied between and into the unfilledopenings, thereby filling such openings residing between spaced-apartbuilding materials. The spaced-apart building materials may be tile ormasonry that are affixed to a subfloor, wallboard or counter. Theunfilled openings may be unfilled joints, cracks and lines residingbetween the spaced-apart building materials (e.g., joints, lines orcracks residing between adjacent tiles).

The UA-HPD grout composition may include 10-40 wt. % of the UA-HPD, and60-90 wt. % of the filler material. In various embodiments of theinvention, the UA-HPD grout composition may include the UA-HPD, firstfiller material (e.g., a quartz filler material), and one or moreadditional filler materials that add desired characteristics andproperties to the UA-HPD hybrid grout. In certain embodiments, thecomposition may comprise 19-23 wt. % UA-HPD, 70-80 wt. % quartz fillermaterial, and a remainder wt. % of the one or more additional fillermaterials. The additional filler materials may include one or more ofthe following constituents: freeze-thaw stabilizer co-solvent,plasticizer, short fibers, glass fibers, an adhesion promoter, apreservative, biocide, cellulose or starch ether, a thickening agent,silica fume, fumed silica, silica fume, a deaerator, defoamer,surfactant, decorative fillers, and any combination of the foregoing.

BRIEF DESCRIPTION OF THE DRAWINGS

The features of the invention believed to be novel and the elementscharacteristic of the invention are set forth with particularity in theappended claims. The figures are for illustration purposes only and arenot drawn to scale. The invention itself, however, both as toorganization and method of operation, may best be understood byreference to the detailed description which follows taken in conjunctionwith the accompanying drawings in which:

FIGS. 1A and 1B show exemplary process flows of preparing aurethane-acrylic hybrid polymer dispersions (“UA-HPDs”) for use in thepresent grouts, grout products and methods of using the same inaccordance with the various embodiments of the invention.

FIG. 2 shows dynamic mechanical analysis (DMA) data comparing a simpleblend with UA-HPDs suitable for use in the various embodiments of theinvention.

FIG. 3 shows tensile strengths of exemplary UA-HPDs suitable for use inthe various embodiments of the invention.

FIG. 4 is a table showing attributes of film coatings made using UA-HPDssuitable for use in the various embodiments of the invention.

FIGS. 5A-B is a table showing various UA-HPD grout formulations inaccordance with the numerous embodiments of the present invention.

FIG. 6 is a table showing one or more embodiments and/or examples ofUA-HPD grout compositions in accordance with one or more embodiments ofthe invention.

FIG. 7 is a table showing one or more alternate embodiments and/orexamples of UA-HPD grout compositions in accordance with variousembodiments of the invention.

FIG. 8 is a table showing still further alternate embodiments and/orexamples of UA-HPD grout compositions in accordance with variousembodiments of the invention.

FIG. 9 is a table showing comparative test results of the UA-HPD groutcompositions of the invention as compared to results of a conventionalone-part grout composition.

DESCRIPTION OF THE PREFERRED EMBODIMENT(S)

In describing the preferred embodiment of the present invention,reference will be made herein to FIGS. 1-9 of the drawings in which likenumerals refer to like features of the invention.

The present invention is directed to a unique, ready to use groutingformulation suitable for use in joining tile, masonry, mosaics and othertypes of building materials, as well as for filling joints and voidsbetween such materials. There are many grouts currently available, witheach grout having its own drawbacks, as discussed above. Whilepolyurethane dispersion (i.e., waterbourne polyurethane) grouts may haveadvantages over cement-based, two- or three-part grouts and evenpremixed acrylic binder grout systems or blends thereof withpolyurethane, such polyurethane dispersions (i.e., waterbournepolyurethane) have disadvantages that in turn generate disadvantages inthe grouts formed thereby.

Disadvantages of polyurethane dispersions are disclosed in the followingreferences, which are discussed herein below: “HYBRID VIGOUR: WaterborneUrethane-Acrylics combine High Performance with Low VOC Content;” Lim,Galgoci, Walker and Yoxheimer; ECJ (05), 24-30, (2005); and“Solvent-Free Urethane-Acrylic Hybrid Polymers for Coatings;” Galgoci,Hegedus, Walker, Tempel, Pepe, Yoxheimer and Boyce; JCT CoatingsTech,2(13), 28-36 (February 2005).

Waterborne polyurethane dispersions (referred to as “PUDs”) have beenused as binders for a variety of one-component coatings for wood (floorsand furniture), plastic (business machine housings), leather, metal, andconcrete. In general, PUDs are prepared by reacting an excess ofdiisocyanate with a polyol, dispersing the resulting prepolymer inwater, and completing the reaction by adding a water-soluble diamine toconsume the residual isocyanate and, thereby, chain-extend theprepolymer to a high molecular weight.

The dispersed PUD particles are usually anionically stabilized, which iscommonly accomplished by incorporating a carboxylic acid-functionalpolyol into the backbone of the polyurethane and neutralizing the acidgroups with a tertiary amine Thus, in many cases, no externalsurfactants are present to contribute adversely to water sensitivity ofPUD-based coatings. PUDs are available in both aromatic and aliphaticvarieties.

One of the main disadvantages of PUDs is their relatively high cost. Inorder to reduce costs, formulators have blended PUDs with an acrylicpolymer emulsion. However, the PUD and acrylic polymer remain asseparate components (i.e., able to be separated and isolated form eachother) within the blended formulation. Further, it has been found thatthe acrylics reduce the overall performance of the PUD binder within thecomposition. On a molecular level, the acrylic polymers are not solublein the polyurethane polymers, such that, the polymers remainphase-separated during use, which may diminish performance behavior.

To overcome the deficiencies of PUDs, and PUD and acrylic polymerblends, urethane-acrylic hybrid polymer dispersions (referred to as“UA-HPD”), have been formulated. U.S. Pat. No. 5,594,065 (to Tien, etal.), which is herein incorporated by reference in its entirety,describes urethane-acrylic hybrid polymer dispersions, which arecommercially available from assignee Air Products and Chemicals, Inc. ofAllentown, Pa. and sold under the trademark Hybridur®. These UA-HPDincorporate both urethane and acrylic polymers into a single dispersion,whereby such constituents are chemically altered into a single, uniquecompound with such constituents being inseparable from each other (cannot isolate one from the other).

UA-HPDs may be formed by different techniques and processes. FIGS. 1Aand 1B show exemplary alternate process flows for preparing a firstUA-HPD (Type 1 hybrid) and a second UA-HPD (Type 2 hybrid). As shown inFIG. 1A, a Type 1 UA-HPD is formulated by first preparing a PUD followedby adding acrylic monomers to the PUD so that an acrylic polymer isformed in the presence of the PUD to generate the UA-HPD. Type 2 UA-HPDsmay be formulated by forming a polyurethane prepolymer and addingacrylic monomers thereto, whereby the mixture is dispersed in water, andthe urethane and acrylic polymerizations are completed concurrently.

The UA-HPD's are unique molecules and not a mere blend of one part withanother part in the composition. It has been found that UA-HPD'sgenerate a gel (via gel testing), have a single broad plateau for glasstransition temperature (T_(g)) test, the polyurethane can not beextracted from the product, and the physical properties thereof arebetter than that of a simple waterbourne polyurethane and acrylicpolymer blend. All of the foregoing factors are evidence ofcross-linking, which is indicative that an UA-HPD undergoes molecularchange (i.e., it is a unique molecule and not a mere blend). Incomparison, it has also been found that waterbourne polyurethane andacrylic polymer blends do not generate a gel (via gel testing), producetwo unique peaks in T_(g) testing, and the polyurethane or acrylic maybe extracted from the blend, all of which are indicative that the twocomponents remain separate in solution with no cross-linking.

FIG. 2 shows dynamic mechanical analysis (DMA) data comparing a simpleblend with different UA-HPD's. As shown, the simple blend has 2 distincttan delta (tan δ) peaks, which correspond to the glass transitiontemperatures (T_(g)) for the phase-separated urethane and acrylicpolymers. The Type 1 UA-HPD hybrid prepared from FIG. 1A shows 2 T_(g)peaks, but the peaks have become somewhat broader, which is indicativeof molecular mixing.

Alternatively, the Type 2 UA-HPD hybrid prepared from FIG. 1B, in whichthe urethane prepolymer and acrylic monomers are homogeneously mixedprior to dispersion and subsequent polymerization, shows only a single,very broad tan δ peak. The single peak, which spans the temperaturerange between the theoretical T_(g)s of the urethane and acrylicpolymers, shows a significant amount of polymer-polymer, wherein it isbelieved these different polymer molecules are intertwined orcross-linked similar to that of an interpenetrating network (IPN). Thisimproved compatibility for the hybrids (especially Type 2) is at leastpartly the result of some molecular-level grafting (cross-linking) ofthe two polymers.

The Type 1 UA-HPD and Type 2 UA-HPD have been used to form filmcoatings, and the resultant coating have exhibited enhanced strengthover that of PUDs or simple blends (e.g., a polyurethane blended with anacrylic polymer). FIG. 3 shows tensile strengths of films prepared fromblends and the Type 1 UA-HPD and Type 2 UA-HPD, which are compared tothat predicted by a linear rule of mixtures. The blend and the UA-HPDhybrids contained equal amounts of the same urethane and acrylicpolymers. As shown, the tensile strength of the blend was found to belower than that predicted by the simple averaging rule. On the otherhand, the hybrid systems show higher tensile strengths than predicted.The Type 1 hybrid system showed slightly higher tensile strength thanpredicted. The Type 2 hybrid was found to have a tensile strengthapproximately equal to that of the polyurethane. The Type 2 hybrid hasthe increased phase morphology of a unique urethane/acrylic polymersystem, as compared to the Type 1 hybrid.

UA-HPDs may be prepared using an aprotic solvent such asN-methylpyrrolidone (NMP). The NMP is required in the polyurethaneprepolymer step to dissolve the dimethylolpropionic acid (DMPA), whichis a crystalline carboxylic acid-polyol that is virtually insoluble inthe polyoldiisocyanate mixture that reacts to form the urethaneprepolymer. The NMP remains in the final dispersion product, with anamount that may range from 3% to 8% in the UA-HPD. NMP is beneficial inthe final product as a coalescing solvent for film formation. However,since NMP and high levels of residual acrylic monomers are undesired dueto odor and regulatory issues, UA-HPDs are also available as NMP-free,low residual monomer UA-HPDs having acceptable workability and resultscriteria.

To date, the use of UA-HPDs has been limited to film or coatingformations. Attributes of test results from such films/coatings areshown in FIG. 4. The present invention extends the use and applicationof the various types of UA-HPDs by providing grouts, grout products andmethods of using such grouts, whereby the grout contains at least aurethane-acrylic hybrid polymer dispersion (“UA-HPD”) as the activebinding agent in combination with one or more filler materials.

While the Type 1 UA-HPDs and Type 2 UA-HPDs are described and discussedherein (as well as those in U.S. Pat. No. 5,594,065), it should beappreciated and understood that the various grouts, grout products andmethods of using such grouts of the invention are not limited to suchUA-HPDs. Rather, any and all current and future UA-HPD formulations maybe implemented in accordance with the various grouts, grout products andmethods of use thereof in accordance with the numerous embodiments ofthe invention.

While not meant to limit the invention, in one or more embodiments apreferred UA-HPD(s) for use in one or more embodiments may include thosesold by Air Products and Chemicals, Inc. of Allentown, Pa., under thetrademark Hybridur®. Again, it should be appreciated and understood thatthe present invention is not limited to the foregoing describedurethane-acrylic hybrid polymer dispersions, and may include any knownand/or to be developed urethane-acrylic hybrid polymer dispersion(s).Such UA-HPD(s) may contain a solvent (e.g., N-methylpyrrolidone (NMP)solvent), or be solvent-free versions of UA-HPDs. The UA-HPD(s) suitablefor use in one or more embodiments of the invention exhibit the hybridnature of being a unique molecule formulated within the polymerdispersion (i.e., it is not a blend or mere mixture of two or moreconstituents).

Referring to the various grouts, grout products and methods of usingsuch grouts in accordance with the invention, the table of FIGS. 5A-Bshow various formulations of the present UA-HPD containing groutcompositions in accordance with different embodiments of the invention.

In one or more embodiments, the premixed grouts and grout products ofthe invention include a urethane-acrylic hybrid polymer dispersion(“UA-HPD”) as the active binding agent in combination with one or morefiller materials. The UA-HPD binding agent may be provided in an amountof about 10%-40% by weight of the total composition. In suchembodiments, the filler materials may be provided in an amount of about60%-90% by weight of the composition. Filler materials may be anymaterial that fills voids between larger particles to improve shrinkage,hardness, reduce porosity, improve water resistance, etc. of the finalgrout. For instance, fillers suitable for use include, but are notlimited to, sand, silica sand, colored silica sand, fine silica, glass,recycled glass, recycled glass filler, limestone (calcium carbonate),minerals, any other known filler, or even combinations of the foregoing.

In one or more embodiments the premixed grouts and grout products of theinvention may include one or more of the additional constituents aslisted in FIGS. 5A-B. In particular, in addition to the UA-HPD andfiller materials, the present grouts may further include a thickener forimproving shelf stability of the grout. The thickening agent minimizesseparation or settling of ingredients within the composition. It alsoimproves rheology or workability of the final grout product. Suitablethickeners include, but are not limited to, cellulose ether, starchether, fibers, silica fume, fumed silica, associative and alkaliswellable thickeners, an acrylic thickener, and the like. Thickeningagents may be present in the compositions of the invention in amountsranging from about 0-3% by weight of the composition.

Decorative fillers may also be provided within the present UA-HPDgrouts. These decorative fillers improve aesthetics of the groutproduct, and may even provide translucency or reflective effects in thefinal cured product. Decorative fillers may include, but are not limitedto, reflective particles, glass or colored beads, dyes, pigments, andthe like. The decorative fillers may be provided in the groutcompositions in amounts ranging from about 0-10% by weight of thecomposition.

In addition, the various UA-HPD grout compositions of the invention mayinclude a variety of alternate binders in addition to the UA-HPDbinders. These alternate binders may be provided in the present groutformulations, in addition to the UA-HPD binder, for reducing costs ofthe resultant grout products and compositions. The alternate binders maybe added in amounts of about 0%-25% by weight of the total composition,and may include blends with conventional binders such as acrylics.Fibers may also be added to the present grout compositions in amounts ofabout 0%-5% by weight. The fibers are added to improve cohesive strengthof the instant wet formulations, improve their strength when cured,reduce shrinkage and even reduce cracking. Various types of fibers maybe added including, but not limited to, polymer or glass fibers ofvarious lengths. The grout compositions may also include polyethylenefibers.

Preservatives or biocides may also be provided in the present groutcompositions. The preservative/biocide component increases the shelflife of the present grout products by inhibiting biological growth.Preservatives or biocides may be present in the compositions of theinvention in amounts ranging from about 0-1% by weight of thecomposition. The compositions may also include one or more fungicidesand/or mildewcides for improving performance of the grout by minimizingbiological growth during use of the grouts, as well as the final curedproduct. Fungicides and/or mildewcides may be present in the grouts ofthe invention in amounts ranging from about 0-1% by weight of thecomposition.

Another constituent that may be added to the UA-HPD grout compositionsof the invention are defoamers. A defoamer reduces air entrainmentduring manufacturing and application. It also improves strength andstain resistance of the final cured grouts of the invention. Defoamersmay be present in the UA-HPD grouts of the invention in amounts rangingfrom about 0-3% by weight of the composition.

The UA-HPD grouts of the invention may further include film forming aids(co-solvents) in an amount ranging from about 0-15% by weight of thecomposition. The film forming aids improve film formation at lowertemperatures, and as such, provide higher strength and hardness. Theymay also improve stability to freezing and thawing of the presentgrouts. Crosslinkers or other reactive components may also be added tothe present UA-HPD grout compositions in amounts ranging from about 0-5%by weight of the composition. These constituents are added to improvehardness, water resistance, chemical resistance, stain resistance, andabrasion resistance.

Adhesion promoters or coupling agents may further be added to thepresent UA-HPD grouts in amounts ranging from about 0-5% by weight ofthe composition. These adhesion promoters or coupling agents improvebonding or compatibility between binder and fillers or substrates. Theinstant UA-HPD grout formulations of the invention may also includestain resistant additives including, but not limited to, wax emulsions,wax particles, fluoro-carbon based particles and emulsions,silicone-based particles and emulsions, hydrophobes such as oleates andstearates, and the like. These stain resistant additives may be added inamounts of 0-5% by weight to improve resistance to water-based and/oroil-based stains, as well as improve water and oil resistance.

Surfactants may be added to the instant UA-HPD grout compositions inamounts of 0-5% by weight of the composition to improve wetting offillers and substrates. These surfactants also help to reduce viscosity,eliminate entrained air, and even stabilize the grout formulation. Watermay be added in amounts of 0-10% by weight to reduce viscosity and actas a diluent. Still further, water retention aids (e.g., celluloseethers, starches, co-solvents, etc.) may be added in amounts of 0-5% byweight to hold or retain moisture within the present UA-HPD groutcompositions during use thereof. By holding or retaining water, thewater retention improve application characteristics and assist cleanup.

The various UA-HPD grouts of the even may also include about 0-5%, byweight, of UV stabilizers, and about 0-5%, by weight, of acids or bases.The UV stabilizers improve resistance to UV light, as well as providefor improved color stability and reduce yellowing or discoloration. Theacids or bases allow for the adjustment of the composition pH to improveformulation stability. Still further, the instant UA-HPD grouts may beinclude anti-freeze components (e.g., glycols, various co-solvents,etc.) in amounts of 0-5%, by weight, to reduce the freezing point of thecomposition for preventing damage thereof during extreme temperatures.Hence, the anti-freeze components also improve storage stability of theinstant UA-HPD grouts.

While the above embodiments disclose various formulations andconstituents that may be added to the instant grout compositions that atleast include an UA-HPD composition, it should be appreciated that theinvention is not limited to such formulations. Referring to FIG. 6, oneor more exemplary embodiments of the grout compositions of the inventionare shown including, by weight percent of the composition: 19.5-23 wt. %UA-HPD (e.g., Hybridur® dispersion); 70-80 wt. % Silica Sand/RecycledGlass Filler (100 Mesh quartz particles) (preferably, 72-80 wt. % or70-78 wt. %); 0.80-1.5 wt. % freeze-Thaw Stabilizer/Co-solvent orplasticizer (preferably, 0.85-0.95 wt. % or 0.8-1.5 wt. %); 0-0.3 wt. %Short Filler/Rheologicial Modifier-Short Fibers (Polyethylene) or glassfibers; 0.14-0.2 wt. % Adhesion Promoter; 0.002-0.005 wt. %Preservative; 0.01-0.02 wt. % Biocide; 0-0.25 wt. % Cellulose Ether orstarch ether; 0-0.20 wt. % Acrylic Thickener; 0-0.06 wt. %Cabosil/Silica Fume; 0.04-0.18 wt. % deaerator, defoamer or surfactant(preferably, 0.12-0.18 wt. % or 0.04-0.08 wt. %); and optionally 0-5 wt.% Decorative Dazzle silica sand/recycled glass filler (100 mesh quartzparticles) (preferably, 72-80 wt. % or 70-78 wt. %); 0.80-1.5 wt. %freeze-thaw stabilizer/co-solvent or plasticizer (preferably, 0.85-0.95wt. % or 0.8-1.5 wt. %); 0-0.3 wt. % short fiber/rheologicialmodifier-short fibers (polyethylene) or glass fibers; 0.14-0.2 wt. %adhesion promoter; 0.002-0.005 wt. % preservative; 0.01-0.02 wt. %biocide; 0-0.25 wt. % cellulose ether or starch ether; 0-0.20 wt. %acrylic thickener; 0-0.06 wt. % fumed silica/silica fume; 0.04-0.18 wt.% deaerator, defoamer or surfactant (preferably, 0.12-0.18 wt. % or0.04-0.08 wt. %); and optionally 0-5 wt. % decorative dazzle fillers.

Still other exemplary embodiments of the invention are shown in FIGS. 7and 8. Referring to FIG. 7, in one or more exemplary embodiments of theinvention the present UA-HPD grouts of the invention may be formed as atranslucent grout product. In these embodiments, the translucent UA-HPDgrouts may include in combination: a first freeze thawstabilizers/co-solvent (e.g., hydrophilic ethane-1,2-diol) in an amountof 0.7-0.95 wt. %; a second freeze thaw stabilizers/co-solvent (e.g.,hydrophobic glycol ether) in an amount of 0.7-0.95 wt. %; an in-canpreservative (e.g., a blend of benzisothiazolin and2-hydroxyethyl-triazine) in an amount of 0.002-0.005 wt. %; a biocide(e.g., Microban™) in an amount of 0.01-0.02 wt. %; cellulose ether (e.g,hydroxyethylcellulose) in an amount of 0-0.25 wt. %; acrylic thickener(e.g, HEUR based rheological modifier) in an amount of 0-0.2 wt. %;anti-settling aid (e.g, modified urea) in an amount of 0.05-0.1 wt. %;UA-HPD (i.e., hybrid polymer dispersion) in an amount of 15-20 wt. %; ade-aearator (e.g., a siloxane based defoamer) in an amount of 0.25-0.5wt. %; and glass filler (e.g., recycled glass) in an amount of 70-90 wt.%. It should be appreciated that any combination of these constituentsmay be implemented in preparing the UA-HPD grouts and UA-HPD groutproducts of the invention, or all of such constituents may be used incombination with each other in the above disclosed weight percentranges.

As shown in FIG. 8, in one or more other exemplary embodiments of theinvention, the UA-HPD grouts of the invention may be formed as scaled-upsanded UA-HPD grout formulations. In one or more embodiments, theseUA-HPD grouts may include at least one or more of the followingconstituents: a first freeze thaw stabilizers/co-solvent (e.g.,hydrophilic ethane-1,2-diol) in an amount of 0.7-0.95 wt. %; a secondfreeze thaw stabilizers/co-solvent (e.g., hydrophobic glycol ether) inan amount of 0.7-0.95 wt. %; an in-can preservative (e.g., a blend ofbenzisothiazolin and 2-hydroxyethyl-triazine) in an amount of0.002-0.005 wt. %; a Biocide (e.g., Microban™) in an amount of 0.01-0.02wt. %; cellulose ether (e.g, hydroxyethylcellulose) in an amount of0-0.25 wt. %; acrylic thickener (e.g, HEUR based rheological modifier)in an amount of 0-0.2 wt. %; anti-settling aid (e.g, modified urea ormodified urea based anti-settling aid) in an amount of 0.05-0.1 wt. %;UA-HPD (i.e., hybrid polymer dispersion) in an amount of 15-20 wt. %; ade-aearator (e.g., a siloxane based defoamer) in an amount of 0.25-0.5wt. %; and sand filler (e.g., colored silica sand) in an amount of 70-90wt. %.

The UA-HPD containing grout compositions of the invention have superiorperformance as compared to mere PUD containing grout compositions. Thevarious UA-HPD containing grout compositions of the invention haveenhanced hardness, abrasion resistance and stain resistance, as well asharden or cure at an efficient and easy to use rate, as compared tocurrently available ready to use grouts (in particular, PUD containinggrouts). The improved performance of the instant UA-HPD containinggrouts is in the unique interpenetrating network microstructure of theurethane-acrylic hybrid polymer dispersions, which is due to theinteraction and grafting on a molecular level between the urethane andacrylic portions.

The various UA-HPD grouts of the invention preferably comprise premixedand/or one-part grout composition mixtures that are easy and ready touse formulations, may be fabricated in a variety of colors, includedifferent decorative features (e.g., sparkles, speckled patterns, etc.),resist to discoloration, fading and staining, and are resistant toabrasions and cracking due to applied stresses. The present UA-HPDgrouts may be used in the installation of a variety of different tiles,masonry and other types of building materials, as well as for fillingjoints and voids between such materials. In use, the present UA-HPDgrouts of the invention may be applied directly from a container,without mixing, onto a substrate (e.g., floor, wall, counter, etc.) tofill openings, spaces, joints, cracks and/or lines residingthere-between.

The premixed UA-HPD grouts of the invention have a workable consistencythat enables such UA-HPD grouts to be applied into and fill thick and/orthin lines and cracks residing between adjacent masonry, particularly,tiles (e.g., ceramic tiles) after such tiles have been affixed (e.g.,with adhesive) to a substrate (e.g., subfloor, wall panel, counter,etc.). A trowel and/or other masonry tools may be used to work theUA-HPD grouts into and fill these lines and cracks. Once worked into thelines and cracks, excess UA-HPD grout material is removed from thesurface of the tile, and the UA-HPD grouts of the invention are allowedto cure over a period of approximately twenty-four hours.

Referring to FIG. 9, numerous different sanded formulation embodimentsof the present UA-HPD grouts were prepared and comparison tested to aconventional one-part premixed waterbourne polyurethane blend groutapplied and cured under the same processing conditions. In the examplecomparative inventive UA-HPD grouts shown in FIG. 9, amounts of selectedconstituents were altered (i.e., +15%, −15%) in the grout formulations,and all allowed to cure under the same processing conditions. Forinstance, in the examples the following constituents were altered +15%,−15%: in examples 1 and 1A thickener wt. %, in examples 2 and 2Acellulose ether wt. %, in examples 3 and 3A anti-settling aid wt. %, inexamples 4 and 4A defoamer wt. %, and in examples 5 and 5A sand fillerwt. %. In examples 6 and 6A, the test UA-HPD grouts were altered byfabricating formulations in different aqueous phases with example 6having +10% solvent and example 6A having −10% solvent.

The comparative grouts were set up for a series of tests to measure thehardness and compressive strengths, including, testing for specificgravity (density), A shore hardness and compressive strength (psi,modified ANSI 118.3 method). The specific gravity (density) was measuredby filling a standard cup of known volume and weight of material in thecup was recorded. For the hardness test, a standard cap was filled withthe material and allowed to harden at ambient temperature for 24 hours.Shore A hardness was then recorded for each tested grout after 24 hours.For the compressive strength test, a standard one-inch cylindrical moldwas filled with the material as per ANSI 118.3. The molds were heatcured for 3 days in a 50 deg. C. oven. The samples were then de-moldedand cured in a controlled temp chamber and tested after 25 days (28 daymeasurement from the day of filling the molds).

The results of FIG. 9 show that the specific gravity of each of theformulas was maintained within a certain range, which indicates that theworkability was kept relatively constant. Also, all of the instantUA-HPD grout formulations had similar consistency for use as a grout.The table shows that the present UA-HPD grouts and grout products of theinvention have both superior hardness after 24 hours and compressivestrength as compared to the tested commercially available one-part waterborne-polyurethane blend grout. The increased hardness measures of theUA-HPD grouts indicates quicker walk over time, or time to traffic. Thecompressive strength of one inch UA-HPD grout cylinders as tested permodified ANSI 118.3 were much higher than that of the commerciallyavailable one-part water borne-polyurethane blend grout. All of thisperformed testing and results shown in FIG. 9 evidences that the instantUA-HPD grouts and grout products of the invention are superior inperformance as compared to the tested prior art water borne polyurethanebased grout.

While the present invention has been particularly described, inconjunction with a specific preferred embodiment, it is evident thatmany alternatives, modifications and variations will be apparent tothose skilled in the art in light of the foregoing description. It istherefore contemplated that the appended claims will embrace any suchalternatives, modifications and variations as falling within the truescope and spirit of the present invention.

Thus, having described the invention, what is claimed is:
 1. A groutcomposition comprising: a urethane-acrylic hybrid polymer dispersion(UA-HPD) binder present in an amount of about 19-23 wt. %, based on aweight of the composition; a first filler material present in an amountof about 70-80 wt. %; and one or more additional filler materials thatadd desired characteristics and properties to said grout, wherein wt. %are all based on a total weight of the grout composition.
 2. The groutcomposition of claim 1 wherein filler material is selected from thegroup consisting of sand, silica sand, colored silica sand, fine silica,glass, recycled glass, limestone, minerals, and combinations thereof. 3.The composition of claim 1 wherein the one or more filler materialscomprise a quartz filler material in combination with one or moreadditional filler materials that add desired characteristics andproperties to said grout.
 4. The composition of claim 3 wherein the oneor more additional filler materials are selected from the groupconsisting of freeze-thaw stabilizer co-solvent, plasticizer, shortfibers, glass fibers, an adhesion promoter, a preservative, biocide,cellulose or starch ether, a thickening agent, silica fume, a deaerator,defoamer, surfactant, and any combination of the foregoing.
 5. Thecomposition of claim 3 wherein the quartz filler material is present inan amount of about 70-80 wt. % based on the total weight of the groutcomposition, with the one or more additional filler materials comprisingthe remainder wt. % of the grout composition.
 6. The grout compositionof claim 5 wherein the additional filler material comprises afreeze-thaw stabilizer co-solvent or plasticizer in an amount of about0.80-1.5 wt. % based on the total weight of the grout composition. 7.The grout composition of claim 6 wherein the additional filler materialcomprises an adhesion promoter in an amount of about 0.14-0.2 wt. %based on the total weight of the grout composition.
 8. The groutcomposition of claim 7 wherein the additional filler material comprisespreservative in an amount of about 0.002-0.005 wt. % based on the totalweight of the grout composition.
 9. The grout composition of claim 8wherein the additional filler material comprises deaerator, defoamer,surfactant each in amounts of about 0.04-0.18 wt. % based on the totalweight of the grout composition.
 10. The grout composition of claim 9further including one or more of the following additional fillermaterials selected from the group consisting of strengthening fibers,short fibers, glass fibers, biocide, fungicide, mildewcide, film formingaids, surfactants, crosslinking agents, coupling agents, celluloseether, starch ether, thickening agent, silica fume, water or a waterretention aid agent, UV stabilizers, acid or base component, decorativefillers, coloring or pigment agent, stain resistant additives, and anycombination of the foregoing.
 11. A grout composition consistingessentially of: urethane-acrylic hybrid polymer dispersion (UA-HPD) as abinder present in an amount of about 19-23 wt. %; a first fillermaterial present in an amount of about 70-80 wt. %; and one or moreadditional filler materials that add desired characteristics andproperties to said grout, wherein wt. % are all based on a total weightof the grout composition.
 12. The grout composition of claim 11 whereinthe first filler material comprises a quartz filler selected from thegroup consisting of sand, silica sand, colored silica sand, fine silica,glass, recycled glass, and any other known filler.
 13. The groutcomposition of claim 11 wherein the one or more additional fillermaterials include one or more constituent selected from the groupconsisting of a freeze-thaw stabilizer co-solvent or plasticizer,adhesion promoter, preservative, deaerator, defoamer, surfactant,strengthening fibers, short fibers, glass fibers, biocide, fungicide,mildewcide, film forming aids, crosslinking agents, coupling agents,cellulose ether, starch ether, thickening agent, silica fume, water or awater retention aid agent, UV stabilizers, acid or base component,decorative fillers, coloring or pigment agent, stain resistantadditives, and any combination of the foregoing.
 14. The groutcomposition of claim 11 wherein the one or more additional fillermaterials at least include freeze-thaw stabilizer co-solvent orplasticizer in an amount of about 0.80-1.5 wt. %, adhesion promoter inan amount of about 0.14-0.2 wt. %, preservative in an amount of about0.002-0.005 wt. %, and deaerator, defoamer, surfactant each in amountsof about 0.04-0.18 wt. %, wherein wt. % are all based on the totalweight of the grout composition.
 15. The grout composition of claim 14wherein the one or more additional filler materials may further includeshort fibers or glass fibers in an amount of about 0-0.3 wt. %, biocidein an amount of about 0-0.02 wt. %, cellulose or starch ether in anamount of about 0-0.25 wt. %, thickening agent is an acrylic thickenerin an amount of about 0-0.20 wt. %, silica Fume in an amount of about0-0.06 wt. %, decorative fillers in an amount of about 0-5 wt. %, andany combination of the foregoing, wherein wt. % are all based on thetotal weight of the grout composition.
 16. A grout compositionconsisting of: urethane-acrylic hybrid polymer dispersion (UA-HPD) as abinder present in an amount of about 19-23 wt. %; a first fillermaterial present in an amount of about 70-80 wt. %; a freeze-thawstabilizer co-solvent or plasticizer in an amount of about 0.80-1.5 wt.%; an adhesion promoter in an amount of about 0.14-0.2 wt. %; apreservative in an amount of about 0.002-0.005 wt. %; a deaerator in anamount of about 0.04-0.18 wt. %; one or more additional filler materialsthat add desired characteristics and properties to said grout, whereinwt. % are all based on a total weight of the grout composition.
 17. Thegrout composition of claim 16 wherein the first filler materialcomprises a quartz filler selected from the group consisting of sand,silica sand, colored silica sand, fine silica, glass, recycled glass,and any other known filler.
 18. The grout composition of claim 16wherein the one or more additional filler materials include short fibersor glass fibers in an amount of about 0-0.3 wt. %, biocide in an amountof about 0.01-0.02 wt. %, cellulose or starch ether in an amount ofabout 0-0.25 wt. %, thickening agent is an acrylic thickener in anamount of about 0-0.20 wt. %, silica Fume in an amount of about 0-0.06wt. %, decorative fillers in an amount of about 0-5 wt. %, and anycombination of the foregoing, wherein wt. % are all based on the totalweight of the grout composition.
 19. The grout composition of claim 16,the one or more additional filler materials consisting of: short fibersor glass fibers in an amount of about 0-0.3 wt. %; a biocide in anamount of about 0.01-0.02 wt. %; cellulose or starch ether in an amountof about 0-0.25 wt. %; a thickening agent is an acrylic thickener in anamount of about 0-0.20 wt. %; silica Fume in an amount of about 0-0.06wt. %; and decorative fillers in an amount of about 0-5 wt. %, whereinwt. % are all based on the total weight of the grout composition. 20.The grout composition of claim 16, the one or more additional fillermaterials consisting of: short fibers or glass fibers in an amount ofabout 0-0.3 wt. %; a biocide in an amount of about 0.01-0.02 wt. %;cellulose or starch ether in an amount of about 0-0.25 wt. %; athickening agent is an acrylic thickener in an amount of about 0-0.20wt. %; silica Fume in an amount of about 0-0.06 wt. %; decorativefillers in an amount of about 0-5 wt. %; a defoamer in an amount ofabout 0.04-0.18 wt. %; and a surfactant in an amount of about 0.04-0.18wt. %, wherein wt. % are all based on the total weight of the groutcomposition.
 21. The grout composition of claim 16 wherein fillermaterial is selected from the group consisting of sand, silica sand,colored silica sand, fine silica, glass, recycled glass, limestone,minerals, and combinations thereof.